Preparation of esters of alpha beta unsaturated carboxylic acids



Patented 28, 1948 Thomas Akron, Ohio, assignors to The B. F.

Company, New York, N. 1.,

' New York.

No Drawing.

' Claims.

ES PATENT OFFICE s'rims or ALPHA mrra UNSATUBATED CARBOXYLIC ACIDS L. Gresham and Forrest w. Shaver,

Goodricha corporation of Application November 28, 1945, Serial No. 831,498

This invention relates to the preparation of esters oftalpha-beta unsaturated ca rboxylic acids such as the alkyl acrylates, and is particularly concerned with the preparation of suchcomwherein All: represents an alkyl radical and R represents hydrogen or a substituent radical.

This reaction does not require any special conditions since it proceeds quite rapidly to produce high yields of the desired ester whenever the V reactants are brought into eflective contact with one another. It is preferable however. in order tov control the reaction in such a manner that highpounds by the reaction of a beta-lactone with a g est yields of the ester may be isolated as such dialkyl sulfate. from the reaction mixture, to add one of the re- It is disclosed in U. S. Patents 2,352,641 and actants to the other reactant while maintaining 2,376,704 to Frederick E. Kiing that esters of althe temperature of the reaction mixture below pha-beta unsaturated carboxylic acids such as about 30 0., preferably from about --30 to the alkyl acrylates may be prepared from a'beta l0 (3., and then to separate the ester formed by distillactone (that is, a lactone or inner ester of a lation. Since many alkyl esters of alpha-beta beta-hydroxy carboxylic acid) having a hydrogen unsaturated acids polymerize quite readily, it is atom connected to its alpha carbon atom, by often desirable .to add a polymerization inhibitor heating the beta-lactone with an alkyl alcohol insuch as hydroquinone to the ester during distillathe presence of a dehydration catalyst such as tion to'prevent its polymerization. If water is sulfuric acid, and then distilling the product. added to the reaction mixture, hydrolysis ofthe This reaction apparently proceeds through the alkyl sulfuric acid formed to sulfuric acid and formation of a beta -alkoxy carboxylic acid from alkyl alcohol, and also partial hydrolysis of the v the beta-lactone and the alcohol, and the dehyester formed to the corresponding alpha-beta undration and rearrangement of the beta-alkoxy go saturated acid, will occur. and on distillation. acid to the unsaturated alkyl ester. when carboth the unsaturated acid and the alkyl ester ried out using beta-propiolactone (also called hythereof are obtained.

dracrylic acid lactone) methanol and sulfuric Any other procedure for reacting a beta-lacacid, for example, methyl acrylate is obtained in tone and a dialkyl sulfate also produces an alkyl about 50% yields. ester of an alpha-beta unsaturated acid. For We have discovered that much higher yields of example, when a mixture of beta-lactone and alkyl esters of alpha-beta unsaturated carboxylic dialkyl sulfate is refluxed in asolvent such as an acids are obtained from such beta-lactones by realkyl alcohol having the same alkyl group as the acting the beta-lactone with a dialkyl sulfate. dialkyl sulfate or an inert solvent for the react- In this event a beta-alkoxy carboxylic acid is apants such as benzene. and the reaction mixture parently not the first-formed reaction product. separatedas by distillation, an alkyl ester of an but rather the reaction is believed to proceed alpha-beta unsaturated acid is secured. In this through an unisolated ester intermediate as repevent, the temperature of reaction is the reflux l resented by the following general equation: 7 temperature of the solvent; hence it is apparent R a R H o R a a H uurps'o. c cc=0 [A1k-o%-o c -c( o-An] 133 131 0 1 o I Beta-lactone I Unisolated intermediate I ("i R a a .ur-o-s-on -o :-c-o-a1r t t A'lkyl sulfuric 'Alkyi ester of alpha-beta acid unsaturated carboxylic acid that the reaction occurs at temperatures considerably above room temperature and as high as C. or higher.

Equimolecular proportions of the beta-lactone and the dialkyl sulfate are generally employed since there is no particular advantage in using an excess of either of the reactants. Such an excess, however, may be present if desired.

To illustrate the invention in specific detail, 72 parts by weight (63 parts by volume; 1 mole) of beta-propiolactone are slowly added to 126 parts by weight (95 parts by volume; 1 mole) of dimethyl sulfate over a period of three hours, keeppeated using di isopropyl sulfate, dibutyl sulfate,

diamyl sulfate, di n-octyl sulfate or any other dialkyl sulfate, the corresponding alkyl acrylate is obtained in about 70 to 90% yield.

In another specific procedure, '75 parts by weight of diethyl sulfate are slowly added to 34 parts by weight of beta-propiolactone in a reaction vessel cooled in an ice bath. The reaction mixture is removed from the ice bath whereupon it spontaneously begins to boil. About parts by weight of water are then added and the mixture distilled under vacuum. The crude distillate is stabilized by addition of a small amount of hydroquinone, washed and dried and then redistilled. The distillate consists of a 67% yield of ethyl acrylate and a 19% yield of acrylic acid. Similarly, other alkyl acrylates are secured when other diallryl sulfates are substituted for diethyl sulfate in this procedure.

The reaction of dialkyl sulfates with betapropiolactone (the simplest possible beta-lactone) to produce alkyl acrylates is the preferred embodiment of the invention because of the low cost of beta-propiolactone and the high yields of alkyl acrylates (which are particularly useful unsaturated esters) thereby obtained. However, other useful embodiments, wherein dialkyl acrylates are reacted with other beta-lactones having a hydrogen atom on the alpha carbon atom to produce other alkyl esters of alpha-beta unsaturated acids, are also included in the generic invention herein disclosed. For example, when betabutyrolactone is reacted with a dialkyl sulfate in the same manner as disclosed hereinabove, an alkyl crotonate is obtained in good yield. Similarly, with beta-isobutyrolactone the product is an alkyl methacrylate; with beta-isovalerolactone the product is an alkyl ester of beta-beta-dimethyl acrylic acid; with alpha-ethyl-betapropiolactone the product is an alkyl ester of alpha-ethacrylic acid and with other saturated aliphatic beta-lactones (i. e. homologs of betapropiolactone) having hydrogen on the alpha carbon atom the products are other alkyl esters of alpha-beta unsaturated acids homologous with acrylic acid. Other lactones of beta-hydroxy monocarboxylic acids having at least one hydrogen on the alpha carbon atom and having cycloalkyl, aryl or aralkyl groups also present, such as beta-cyclohexyl-beta-propiolactone, beta-phenylbeta-propiolactone, beta-benzyl5beta-propi0lactone and alpha-phenyl-beta-propiolactone, are also utilizable as the beta-lactone reactant, a solvent preferably being present in this case. All

4 of the above-mentioned beta-lactones are of the eneral structure wherein R is hydrogen or an unreactive hydrocarbon group (i. e., a hydrocarbon group free from aliphatic unsaturation) and may be prepared in the manner described in U. S. Patent 2,356,459 to Frederick E. Kiing. Still other beta-lactones having at least one hydrogen on the alpha carbon atom are known and are also contemplated by this invention. Among these are beta-lactones of unsaturated beta-hydroxy carboxylic acids, monobeta-lactones of dicarboxylic acids and dilactones of dicarboxylic acids in which at least one of the lactones is beta examples of which includes betabeta-dimethyl-beta-propiolactone alpha carboxylic acid and the beta-delta-dilactone of citrylidene malonic acid, all of which, like the beta-lactones before mentioned, are, except for carbonoxy structure t 0 composed exclusively of hydrogen and carbon atoms. Still other beta-lactones containing hydrogen on the alpha-carbon atom also contain,

in addition to carbonoxy structure and hydrogen and carbon atoms. other elements such as oxygen,

I nitrogen, sulfur and halogen present in essentially unreactive structure such as nitro groups and ether linkages or in radicals containing reactive hydrogen such as amino and hydroxy. Examples of such latter beta-lactones include alpha or beta-nitrophenyl-beta-propiolactone; beta- (o-nitro-m-chlorophenyl) beta propiolactone; beta-(o-nitro-m-methoxyphenyl) beta propiolactone; alpha-hydroxy-beta-phenyl beta propiolactone and alpha-chloro-beta-propiolactonel It is thus seen that the invention includes the reaction of any of the generic class of beta-lactones having at least one hydrogen atom connected to the alpha carbon atom with any of the generic class of dialkyl sulfates to form alky-l esters of alpha-beta unsaturated acids, in accordance with the general equation set forth hereinabove.- Accordingly, it is not intended that the invention be limited to the specific details described herein, but only as defined by the spirit and scope of the appended claims.

We claim:

1. The method of preparing an alkyl ester of an alpha-beta unsaturated carboxylic acid which comprises bringing a dialkyl sulfate in which the two alkyl groups are identical and contain from 1 to 8 carbon atoms, and a beta-lactone of the formula wherein each R is a member of the class consisting of hydrogen and alkyl, cyclo-alkyl, aryl and aralkyl hydrocarbon radicals containing less than 8 carbon atoms, into reactive contact with one another at a temperature below about 30 C. and then distilling the reaction mixture.

2. The method of preparing an alkyl acrylate which comprises. admixing a dialkyl sulfate in which the two alkyl groups are identical and contain from 1 to 8 carbon atoms, and betapropiolactone at a temperature below about 30 6., and then distilling the reaction mixture.

3. The method of preparing methyl acrylate which comprises admixing dimethyi sulfate and beta-propiolactone at a temperature of about 30 to 10 C., and then vdistilling the reaction mixture.- V

4. The method of preparing ethyl acrylate which comprises admixing diethyl sulfate and beta-propiolactone at a temperature of about -30 to 10 C., and .thendistilling the reaction mix- 10 ture.

5. The method of preparing an alkyl acrylate which comprises adding betaepropiolactone to a dialkyl sulfate. in which the two alkyl groups are identical and contain from 1 to a carbon atoms at a temperature of about -30 to 10 C., and then distilling the reaction mixture.

1 THOMAS L. GRESHAM.

FORREST W. SHAVER.

REFERENCES crran The following references are of record in the file of this patent:

UNITED STATESv PATENTS Number Name Date 2,352,641 Kung I July 4, 1944 2,376,704 Kung II May 22, 1945 

